LAUSR

HYPOTHESIS Mass transport critically controls the performance of colloidal metal-polymer sensors. We hypothesize that molecular-level pair interactions, such as electric, steric, and specific binding effects, govern the mass transport and, in return, the characteristic time of these sensors. THEORY Here we present a simple theory guided by experimental data to examine the sensing performance of two usually encountered archetypal metal-polymer sensors, namely (1) core-shell and (2) yolk-shell architectures. For this purpose, we use the static reactive density functional theory framework, determining how (i) charge, (ii) size, and (iii) non-covalent binding factors modulate the characteristic time. FINDINGS We show how an interplay between diffusivity and partitioning governs the sensing time of the sensors, where an anti-correlation cancellation between them renders the time non-trivial. Our study demonstrates that the convoluted substrate-hydrogel shell interaction controls the characteristic time of these colloidal sensors, especially when the sensors are in a collapsed state. Notably, the substrates with a high dipole moment tend to equilibrate greatly, but undesirably, at the shell-solution interface. With this, we encourage the formation of a metastable sorption state.